Temperature control system



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Decl, 1970 c; G. HousER ETAL TEMPERATURE CONTROL SYSTEMk Filed Nov. l2. 1968 A TTORNEVS United States Patent O 3,544,540 TEMPERATURE CONTROL SYSTEM Clarence G. Houser and Jack E. Hoskins, Bartlesville,

Okla., assignors to Phillips Petroleum Company, a corporation of Delaware Filed Nov. 12, 1968, Ser. No. 774,945 Int. Cl. C08f 1/88 U.S. Cl. 260-94.9 6 Claims ABSTRACT OF THE DISCLOSURE A method and apparatus is provided for the introduction of liquid solvent to a polyolen ash chopper zone so as to control the temperature of the flash chopper zone and the polymer therein. Introduction of the liquid solvent to the ash chopper zone is regulated in response to the work load on the motor providing power to the chopper means in the flash chopper zone.

BACKGROUND OF THE INVENTION This invention relates to the production and recovery of normally solid polymers. In one aspect it relates to a process for the recovery of a normally solid polymer from a solution thereof. In another aspect it relates to a novel method for controlling the temperature in a solution flash zone wherein there is being produced a substantially solvent-free solid polymer from a solution thereof in a solvent.

Several different processes are known in the art for the production of normally solid polymers, such as polyethylene, polybutadiene and polystyrene. In many of the known processes, the polymer is initially obtained in the form of a solution in the solvent and must be recovered therefrom. Recovery can be effected by different methods, such as solvent vaporization, which leaves the polymer as a nonvolatile residue, and cooling of the solution to cause precipitation of the polymer, which is subsequently recovered by filtration. vaporization processes for solvent removal are accompanied by diiculty in removing the last traces of solvent from the polymer. This diiculty arises from the fact that `as the solution becomes more and more concentrated, its viscosity increases. Heat transfer is correspondingly retarded and, if proper control is not exercised, the polymer may be thermally decomposed as a result of unduly high residence times in recovery equipment at high localized temperatures. It is highly desirable to free the polymer from the solvent insofar as completely as possible because small amounts, e.g., a few weight percent, of solvent in the polymer forms bubbles upon extrusion of said polymer, and consequently cavities when the polymer is heated preparatory to molding.

In addition to the removal of the solvent it is also desirable that the bulk density of the polymer product s controlled. Polymer having a light bulk density has been found to have a tendency to bridge in the system and ultimately results in the plugging of the polymer storage zone. In addition, a more dense polymer can be handled in smaller equipment. For example, doubling the density makes it possible to decrease drying equipment to one-half its usual size. In addition to plugging, polymer having irregular bulk density further presents a problem in maintaining a constant feed rate to the polymer extruder utilized for the further processing of the polymer.

This invention is concerned with the recovery of polymer from solution by ash vaporization, i.e., a hot solution of the polymer under considerable pressure is passed into a low pressure chamber where most of the solvent vaporizes, leaving the polymer as a solid precipitate. Performance of the flash operation i.e., the extent of solvent vaporization in the dash chamber and final temperature of the precipitated polymer is dependent on several factors including (1) temperature of the polymer feed solution passed to the ash chamber (2) polymer concentration in the feed solution, and r(3) pressure in the ash chamber. It has been found possible and desirable in recent polymer production developments to increase the polymer concentration in the solution produced in the reactor and subsequently passed to the flash chamber-this is desirable because the quantity of solvent recycle per quantity of polymer produced is greatly reduced. But as the polymer concentration in the solution passed to the flash zone has increased, the temperature within the ilash zone and the temperature of the precipitated polymer has increased to the melting point of the polymer. This is highly undesirable as the resulting tacky polymer sticks to the chopper much like taify candy, and production of ysolid polymer particles with high bulk density becomes impossible. Control of the temperature in the ilash zone by an independent means has thus become necessary in order to operate with the desirably high polymer concentration in the feed solution.

It has been found that when the temperature in the ash zone reaches the melting point of the polymer, the power input to the chopper motor suddenly increases by an appreciable amount. This is because the polymer has become tacky, tending to foul the chopper, and hence more power is required to rotate the chopper. Measurement of power input to the chopper motor has thus been found to be an excellent indication of temperature Within the ilash chamber and thus can be used to control said temperature.

THE INVENTION It is thus an object of this invention to provide an improved process for the recovery of solid polymer from solution.

Another object of this invention is to provide a process for achieving control of the temperature in a polymer recovery zone wherein solid polymer is recovered from solution.

A further object of this invention is to provide a process for the control of liquid solvent to a polymer recovery zone so as to control the temperature of the polymer therein. i

A still further object of this invention is to provide a control system for the introduction of liquid solvent into a polymer recovery zone.

Other objects, advantages and features of this invention will be apparent to those skilled in the art from the following description, the drawing, and the appended claims.

In accordance with the present invention we have discovered that the temperature in the flash chopper zone wherein polymer is being recovered from solution can be controlled by the introduction of liquid solvent therein responsive to the work load of the motor utilized for powering the chopper means in the ash chopper zone.

The present invention thus provides an improved process and apparatus by which polymer can be recovered from solution thereof by vaporization of the solvent without thermal decomposition of the polyment. The invention also permits utilization of solutions containing high polymer concentrations in a recovery operation 3 whereby solid particles of high bulk density polymer are obtained.

The overall process of the present invention is effected as follows. In a first stage, a solution of polymer in solvent is flashed in a flash comminution zone maintained under pressure and below the melting point of the polymer so as to remove a major portion of the solvent and obtain dense solid polymer particles. The flash zone has associated therewith a chopping means wherein the solid concentrate is reducedV to a predetermined size. In a second stage the resulting sized polymer particles are treated for additional solvent removal in a solvent removal zone which is operated at a lower pressure than the first-stage Y flash comminution zone. The resulting polymer is thereand substantially all of the remaining solvent is removed Vfrom the polymer.` The resulting, essentially solvent-free polymer is recovered as product. l t

The melting point of the polymer will vary, depending on the physical and chemical nature and origin of the polymer. Polyethylenes ordinarily range in melting point from about 210 to about 260 F. The polyethylenes prepared by the process of Hogan and Banks, U.S. Patent 2,825,721, ordinarily have melting points in the range of 240 to 260 'F. but can have melting points outside this range. It is, however, essential to the recovery of the desired solid polymer to maintain the temperature of the polymer in the first flash comminution orchopping zone below the melting point .of the particular polymer being recovered therein from solution.

The recovery process of this invention is particularly applicable `to the recovery of a polymer produced in a process ofthe type disclosed and claimed in the aforementioned Hogan and Banks patent, wherein an aliphatic l-olelin having a maximum chain length of 8 carbon atoms and no branching nearer the double bond than the 4position is subjected to polymerization conditionsin the presence of a catalyst comprising chromium oxide, of which a portion of the chromium is initially hexavalent, associated with at least one oxide selected from the group consisting of silica,.alumina, zirconia and thoria. The process of this invention is lparticularly applicable to the recovery of polymer from a solution thereof having a concentration of polymer therein in the range of 15 to 60 percent. One such solution to which the invention is particularly applicable is that of a polyethylene. Polymers `-so recovered are useful for fabrication into pipe, tubing, electrical insulation and water-resistant wrappings, as.' more fully set forth in the above-cited patent.

In one modification of the overall process of this invention, approximately to 75 percent of the solvent is `vaporized `in a preliminary concentration zone, from 50 to 99 percent of theV remaining solvent is vaporized in the rst flash comminution zone, from 25 to 75 percentof the remaining solvent is removed in .the second stage of this invention wherein a the resulting concentrate of polymer solution containing from .l5 to 60 weight percent polymer is passed to the first stage ash comminution zone which is maintained at a temperature in the range of 150v to 250` F. and below the melting point of the polymer and at a positive pressure in the range of 15 to 50 p.s.i.a. The resulting polymer, in the form of a sized llui, is then passed to a second stage solvent removal flash zone which is oper: ated at a temperature in the range of 150 to 250 F.

and below the melting point of the polymer and at a pressure in the range of l5 to 25 p.s.i.a. and preferably at least 5 p.s.i. below that of the iirst stage ash treating zone. The polymer is thereafter passed to a heated, polymer purge zone which is operated at a temperature in the range of to 250` F. and below the melting point of the polymer and at a pressure in the range of 15 to 25 p.s.i.a. The polymer is then passed to a second purge zone preferably operated under the same conditions of temperature and pressure as the first purge zone. The polymer is agitated in the second purge zone and contacted with an inert gas wherebyessentially all of the remaining solvent is removed. The resulting polymer'flulf having a predetermined bulk density can thereafter be stored Vand/or further treated in conventional apparatus for the formation of filament, pellets or other desired shapes.

In a further embodiment of the invention wherein a high-solids reactor is employed to produce the polymer, the preliminary evaporation step is omitted as the polymer solution obtained fromv the reactor is already at a relatively high concentration of l5 to 60 percent.

The process of this invention can be conducted in evaporators or vacuum dash tanks, the general construction of which is well known lin the art. However, certain special features are involved in the construction of the flash apparatus. Since it has been found that the bulk density of the polymer formed by ashing can be controlled responsive 'to the temperature maintained in the ash zone, control of this temperature and thereby the bulk density of the polymer is provided by novel means, as will be described herein.

As shown in FIG. l ,of the drawing, solvent enters through inlet 2 and is mixed with catalyst supplied from storage 3. The catalyst can be, for example, chromium oxide supported on silica. The catalyst particle size is sufficiently small to facilitate the formation of a slurry of catalyst in the-solvent. The catalyst-solvent slurry passes into reaction zone 4. The bulk of the solvent is passed to the reactor thru line 2. Ethylene and another olefin such as butene-l enters the system through inlet 5 and passes into the reaction zone 4 wherein it is mixed with thecatalyst and the solvent at a temperature, for example, of approximately 280" F. The solvent can be cyclohexane, octane, or other suitable solvents. The proportions of solvent and ethylene are so adjusted that the concentration of polymer inthe reactor does not exceed approximately 15 percent and preferably is in the range from 5 to 10 weight percent. However, when a high-solids reactor is employed as described hereafter, the polymer concentration is generally aboutf30 to 60 weight percent. The pressure in the reaction zone 4 is sufficient to maintain the solvent substantially in theiliquid phase and can be, for example, 500 p.s.i.a. The reaction mixture is maintained in a state of turbulence so that the catalyst is maintained in a substantially uniform suspension or slurry in the reaction mixture. This turbulence can be obtained by j et action of incoming monomer through inlet 5V and/ or by the use of a mechanical stirrerindicated by the numeral 6 and driven by motor M. The reaction zone eluent which comprises a mixture of polymer, solvent, and suspended catalyst, together with small amounts of unreacted and/or inert gas, is passed through conduit 7 and heater 8 to dissolution zone 9. Additional solvent can be added, if desired, in order to adjustthe concentration to a suitably low value,` previously stated, so that the viscosity is not too high for eicient catalyst removal. In dissolution z one 9, the mixtureis maintained in a state of turbulence as, for example, by'rmeans of a mechanical stirrer 13' driven by a motor' M and the temperature is maintained, for example, by the use of heater 14, at from 300 to 400 F., i.e., somewhat higher than that utilized in reaction zone 4. The pressure is suicient to maintain the solvent substantially in the liquid phase but is preferably lower than that in reaction zone 4 to facilitate the evolution of dissolved gas, including unreacted ethylene, which is vented through outlet 15. Heater 14 is of any suitable design known in the artfor example, it can be a steam coil or an electric immersion heater. Eliluent from dissolution zone 9 passes through conduit 10 t0 solids removal zone 16. The material passed through conduit 10 is a homogeneous solution of substantially allof the polymer in the solvent, which solution contains suspended solid catalyst. Solids removal zone 16 comprises any suitable equipment or combination thereof known in the art for the removal of suspended solids from liquids. For example, it can be a ilter or a centrifuge or both. It should be suitable for operation under pressure in order to maintain the solvent in the liquid phase during the filtration. Catalyst removed is withdrawn from the system through conduit 17. 'Ihe withdrawn catalyst can be regenerated or reactivated, if desired, and recycled to catalyst storage zone 3 by means not shown in the drawing. The solution which has been freed of suspended catalyst solids is passed through conduit 18 to preliminary evaporation zone 19 which is ordinarily in the form of a flash evaporation tank and is operated, for example, at a temperature of 290 F. and a pressure of 33 p.s.i.g. Approximately half of the solvent is evaporated in zone 19, and the evaporated solvent is passed through conduit 20 and condenser y21. The condensed solvent is then returned through conduits 22 and 2. The concentrated residue from evaporation zone 19 is passed through conduit 23, pump 24 and heat exchanger 25 wherein the temperature is raised, `for example, to 310 F. yPart of the solution is returned through conduit 26 to evaporation zone 19. This mode of, operation allows outside heating of the unvaporized material from evaporation zone 19 and is a preferred method of supplying heat to said zone, since it is ordinarily impractical to supply heat efliciently directly to the interior of zone 19.

The remainder of the unvaporized material is passed through conduit 27 to a flash chopper having a comminution zone 29 which is in open association with a zone 28. Both zones 28 and 29 are maintained at the same conditions of temperature and pressure. Thus the zones are operated, for example, at a temperature of 150 to 250 F. but below the melting point of the polymer and at a pressure of 16 to 50 p.s.i.a. The solution entering ash comminution zone 28 has a concentration, for example, of 30 to 60 weight percent of polymer in solvent. Comminution zone 28 has therein a knife carrying member 29 with three or morearms, each of which carries a knife blade. Screen 30 is provided of appropriate size openings to retain the solid polymer in zone 28 until the desired polymer particle size as determined by the size of the screen openings is obtained by means of the chopper.

The sized solid polymer particles are then passed by means of rotary valve 31 into a second stage solvent removal zone 32 which is maintained at a temperature in the range of 150 to 250 F., below the melting point of the polymer and at a lower pressure than that of zone 28 and generally in the range of to 25 p.s.i.a. Disengaging tank 33 is provided in association with the solvent removal zone 32 and serves to permit liberation of the vapors thru overhead line 34 without entraining any of the polymer. Generally from 25 to 75 percent of the remaining solvent is removed from the polymer uif in zone 32.

The resulting sized, essentially solvent-free polymer material is thereafter passed to a first heated purge zone 35. Inert gas such as nitrogen or ethylene monomer is introduced through line 36 into the zone 35 so as to assist in removing additional solvent from the polymer particles.

After purging in zone 35, the polymer particles are passed through a conduit 37 containing rotating valves 38 and 39 and then into a jacketed vertical, stirred purge column 40. In this column the polymer is again treated countercurrently with an inert purge gas, introduced via line 41, such as nitrogen or superheated steam for substantially complete removal of residual solvent. Purpose of valves 38 and 39 is to prevent intermixing of the different purge gases used in purge zones 35 and 40. The level Within zone 40 is controlled by level controller 41 which is operatively connected to motor 42 and discharge valve 43 and thereby regulates the rate of polymer from the second stage purge zone 40.

The material from purge zone 40 is thereafter recovered as substantially solvent-free polymer ilutf having a predetermined bulk density and passed by means of conduit 48 to polymer storage zone 49 or directly to other processing apparatus not shown for further handling. For example, the polymer uft' can be introduced into a conventional polymer extruder wherein it is converted to strands of polymer which are thereafter cut to form pellets, rods, or the like.

While the invention has been described with a single first Hash comminution chamber 28 in association with said second ash chamber, it is within the scope of the present invention to utilize more than one such ash comminution zone in association with the second flash zone.

In keeping with the present invention the bulk density of the polymer particles discharged through valve 43 is controlled and the production of a solid product in chambers 29 and 28 is assured 5by controlling the temperature in comminution zone 29 by manipulating valve 45 in response to the Work load on chopper motor 73 as described in more detail in FIG. 2.

The manipulation of valve 45 permits liquid solvent to be introduced into the ash chamber through conduit 52. The liquid solvent thus introduced vaporizes in the Warm, low pressure zone 29 and thus lowers the temperature of the zone.

As shown in FIG. 2, the control system for maintaining temperature in chopper zone 29 comprises motor valve 45 in solvent line 52, an indicating ow transmitter 60 sensitive to the ow of solvent through line 52, and a recorder-controller 62 which controls the amount of opening of valve 45. The set point of recorder-controller 62 is manipulated by a second recorder-controller 64 which compares the actual power consumed by motor 72 with the desired power input. Controller 64 receives a pneumatic signal from electro-pneumatic transducer y66 which passes through pulse damper 68.

One coil of transformer 70 is in circuit with and sensitive to the power or current being consumed by motor 72 and the other coil of transformer 70 is in circuit with transducer 66 so that, as the power or current required to rotate chopper 74 Varies, the current owing through transducer 66 also varies and the pneumatic signal emitted by transducer 66 is varied proportionally. In this manner, variations in current or power requirements are transmitted though the control system so as to vary the opening of valve 45 and, therefore, the flow rate of solvent to the flash chopper zone.

Thus in operation of the control system of this invention, since an increase in temperature in ash chamber 29 to the melting point of the polymer results in an increase in the power or load to motor 72 due to the increase in tackiness of the polymer being chopped in the chamber 29, this measured increase in load Will cause valve 45 to be opened so that additional liquid solvent can be introduced to the Iflash chopper system 29. Conversely, as the power requirement for motor 72 is reduced with indicates a more solid polymer being comminuted by the chopper the control system effectsa closing of valve 45 to reduce the ow of liquid to chamber 29. In this manner there is obtained a control over the temperature conditions in chamber 29 which will permit formation of solid particular particles of polymer.

In addition, in a further aspect of this invention, pressure can be controlled in the ash chopper by the addition` thereto of solvent vapor or some other inert gas from any source thereof such as from zone 19 via line 54 in response u Vdetermined pressure in the system by regulating valve 56 which permits introduction of the solvent vapor or inert gas.

The solvent vaporized in the steps according to this invention can be condensed, combined and recovered, for example, for recycling to the polymerization reaction.lIf desired a portion of the solvent removed from the flash zone after condensing can be returned to the ash zone to assist in maintaining the temperature therein in keeping with the concept of this invention. l

The following example Vis presented to i more fully describe the invention, but it is not intended that it should me construed as limiting the invention thereto.

EXAMPLE reactor pressure maintained at about 465 p.s.i.a. A solution containing `40 weight percent polymer was continuously removed from the reactor and passed via pipes 60 and 61 without treatment directly into Hash-chopper zone 29. When operating zone 29 at a pressure of 10 to 15 p.s.i.g. in order to achieve nearly complete vaporization of the solvent in` thepolymer feed solution `it was found in the pilot plant, tests that the temperature of the precipitated polymer inthe zone was so high and the polymer became tacky, fouled the chopper, and increased the power input of motor 72.aboveits rated capacity of horsepower. Operation under these conditions not only did not produce `the desirable hard, high-density solid polymer particles, but was essentially impossible, because motor 72 was overloaded. By injecting 8 lb./hr. of liquid n-hexane into chopper zone 29 via pipe 52 it was found that the power `input to motor 72 was reduced to only 0.1 horsepower and `satisfactory hard, high-density solid particles of polymer were produced. It was thus found that a pneumatic signal equivalent to 0.1 horsepower could be applied to controller 64 to obtain automatic control of solvent injection via valve A45 into chopper zone 29. During periods when theV temperature and/or polymer concentration of the polymer solution `passing to chopper zone 29 changes suiciently yto again cause partial melting of polymer. in the chopper zone, the increase in power input to motor 72 is, immediately determined by transducer 66 which takes corrective action by passing addition solvent to zone 29 via units 68, 64, and 62. By thus maintaining power input to motor 72 at a constant value by varying the rate of solvent passage to zone 29, l

satisfactory performance of chopper zone` 29 isassured despite slight variations in the polymer solution passed to zone `29 as caused by variaitons and/or upsets in reactor 4. The particles thus produced in zone 29 pass through sizing screen30 into chamber 28 wherein solvent vapor is passed `overhead through valve 45 and the particles pass through rotary valve 3 1 into chamber 33. Chamber 28 operates at about thesame conditions as zone 29, i.e.,Y about 195 F. and 10 to 15 p.s.i.g. Chamber 33 operates at a lower pressure, ie., about Oto 10 p.s.i.g., for the purpose of obtaining additional vaporization of residual liquid solventrThe resulting polyethylene particles with a bulk density of l0 to 15 lb./ft.3 are passed to purge zone 35 consisting of a conveyor dryer wherein they are countercurrently contacted with gaseous ethylene or inert gas for removal of additional solvent. After purging with ethylene the solid polymer particles are passed through two lock valves 38 and 39 into vertical purge column 40 containing a stirring device. The vertical column operates 'at 190 F. and 18 p.s.i.a. and has 240 F. steam (must be superheated to prevent condensation) or inert gas such as nitrogen passing upward through the column countercurrent to the descending polymer. This additional purging reduces the residual solvent to a negligible concentration. Purpose of the lock valves, previously mentioned, is. to preventmixing of the different purge gases used in the auger-conveyor purge unit and the vertical stirred purge unit. The polymer passes from the stirred unit to storage, thence to conventional extrusion and to sales.

Pressure in zone 29 may be increased by passing solvent vapor through pipe 54 by use of controller 53.- It is sometimes desirable to thus increase the pressure in zone 29 in order to increase the bulk density of the polymer particles. It is thus possible to control both pressure and temperature of zone 29 by independent methods and obtain an optimum product.

Although the process of this invention has been described in connection with particular polyethylene procby means of cooling jackets and interior cooling coils and esses, it is clearly not limited thereto but is also applicable to the recovery of any normally solid thermoplastic polymer from a solution thereof in a solvent. Thus, the process is also applicable to solutions of polybutadienes, especially hydrogenated polybutadienes as described in U.S. Patent No. 2,864,809 by Jones and Moberly, polystyrenes, polypropylenes, polyisobutylenes, and polyethylenes produced by processes other than` that of the type described herein, as well as to therecovery of halogenated poleythylenes. Also, the process is not limited tothe recovery of polymers from saturated hydrocarbon solvents but is applicable wherein solvents such as chloroform, carbon tetrachloride, carbon disulfide and aromatic hydrocarbons and derivatives thereof are used as solvents.

The essence of this invention is that'a normally solid thermoplastic polymer of a desired bulk density can be recovered substantially free from a solvent containing same by a process which comprises evaporating a substantial portion of the solvent at a temperature below the melting point of the polymer while simultaneously choppingvor comminuting same, and wherein the temperature of the zone in which this evaporation and chopping is carried out is controlled by the addition of liquid solvent to same as required.

Reasonable variations and modifications of this invention can be made or followed, in view of the foregoing, without departing from the spirit or scope thereof.' We claim: l

1. In a process forrecovering a normally solid thermoplastic polymer from a solution thereof in a solvent which process comprises removing a substantial portion of said polymer from said solution while comminuting same in a ash chopper zone maintained under pressure and at a temperature below the melting point of said` thermoplastic polymer and wherein the temperature in said'ash chopper zone is maintained below that melting point of said thermoplastic polymer bythe introduction of additional liquid solvent to said flash zone, the improvement which comprises sensing the load' on the chopper motor and adding additional liquid solvent when the motor load suddenly increases indicating that the flash zone temperav density of the polymer vobtained as a product of the process is controlled by regulating the temperature in said Hash Z011@ whereby an. increase insaid, temperature results 10 in an increase in the bulk density of the polymer and a References Cited decrease in the temperature results in a decrease in the UNITED STATES PATENTS bulk density of the polymer.

5. A process according to claim 1 wherein the ash lslggi'n zone is operated at a temperature in the range of 150 to 5 3 457 248 7/1969 Cunningham et al. 260 93.5 250 F. and at a pressure in the range of 16 to 50 p.s.i.a.

6. A process according to claim 1 wherein a solution JOSEPH L SCHOFER, Primary Examiner containing about 15 to 60 Weight percent of a polymer s. M. LEVIN, Assistant Examiner of ethylene in n-hexane is introduced to said rst ash zone which is maintained at a temperature of 195 F. 10 US CL X-R- and a pressure in the range of 10 to 15 p.s.i.g. 26o- 88.2, 935, 93,7, 94,7, 94,3 

